JP2002220214A - Method for manufacturing carbon nano tube - Google Patents
Method for manufacturing carbon nano tubeInfo
- Publication number
- JP2002220214A JP2002220214A JP2001014981A JP2001014981A JP2002220214A JP 2002220214 A JP2002220214 A JP 2002220214A JP 2001014981 A JP2001014981 A JP 2001014981A JP 2001014981 A JP2001014981 A JP 2001014981A JP 2002220214 A JP2002220214 A JP 2002220214A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- organic solvent
- carbon nanotubes
- metal
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 22
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 239000011882 ultra-fine particle Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 150000002736 metal compounds Chemical class 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 239000003093 cationic surfactant Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000004530 micro-emulsion Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- UMGXUWVIJIQANV-UHFFFAOYSA-M didecyl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC UMGXUWVIJIQANV-UHFFFAOYSA-M 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- -1 ferrocene Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 102000003729 Neprilysin Human genes 0.000 description 1
- 108090000028 Neprilysin Proteins 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 101000701286 Pseudomonas aeruginosa (strain ATCC 15692 / DSM 22644 / CIP 104116 / JCM 14847 / LMG 12228 / 1C / PRS 101 / PAO1) Alkanesulfonate monooxygenase Proteins 0.000 description 1
- 101000983349 Solanum commersonii Osmotin-like protein OSML13 Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000004075 acetic anhydrides Chemical class 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 229960004670 didecyldimethylammonium chloride Drugs 0.000 description 1
- XRWMGCFJVKDVMD-UHFFFAOYSA-M didodecyl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC XRWMGCFJVKDVMD-UHFFFAOYSA-M 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、カーボンナノチュ
ーブの製造方法に関するものである。[0001] The present invention relates to a method for producing carbon nanotubes.
【０００２】[0002]
【従来の技術】カーボンナノチューブの製造方法の１つ
として、超微粒子状遷移金属からなる触媒の存在下で有
機炭素原料の蒸気を熱分解させる化学蒸着法（ＣＶＤ）
が知られている（特開平９−３１７５７号公報）。しか
しながら、この従来法の場合、その触媒は、フェロセン
等の金属錯体を熱分解することによって調製されている
ため、その触媒粒子の大きさの制御が困難であり、その
結果、製造されるカーボンナノチューブの太さを制御す
ることも困難であった。さらに、前記の従来法では、直
径が１ｎｍ程度の細いカーボンナノチューブの製造は非
常に難しいものであった。2. Description of the Related Art As one method of producing carbon nanotubes, a chemical vapor deposition (CVD) method is used in which a vapor of an organic carbon raw material is thermally decomposed in the presence of a catalyst composed of an ultrafine transition metal.
Is known (Japanese Patent Application Laid-Open No. 9-31757). However, in the case of this conventional method, since the catalyst is prepared by thermally decomposing a metal complex such as ferrocene, it is difficult to control the size of the catalyst particles. It was also difficult to control the thickness of the paper. Furthermore, in the above-mentioned conventional method, it is very difficult to produce a thin carbon nanotube having a diameter of about 1 nm.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、カーボンナ
ノチューブの太さの制御が容易で、しかも微細直径のカ
ーボンナノチューブの製造が可能なカーボンナノチュー
ブの製造方法を提供することをその課題とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing carbon nanotubes which can easily control the thickness of carbon nanotubes and can produce carbon nanotubes having a fine diameter.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を重ねた結果、本発明を完成する
に至った。即ち、本発明によれば、０．４〜３０ｎｍの
粒径を有する触媒超微粒子を有機溶媒中に分散させて形
成した触媒分散液を、７００〜１５００℃に加熱した加
熱炉内に供給して、該有機溶剤を分解させることを特徴
とするカーボンナノチューブの製造方法が提供される。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, a catalyst dispersion formed by dispersing ultrafine catalyst particles having a particle diameter of 0.4 to 30 nm in an organic solvent is supplied to a heating furnace heated to 700 to 1500 ° C. And a method for producing carbon nanotubes, characterized by decomposing the organic solvent.
【０００５】[0005]
【発明の実施の形態】本発明で用いる触媒は、カーボン
ナノチューブの合成に触媒作用を有するものである。こ
のような触媒としては、通常、遷移金属が用いられる。
この触媒金属としては、特にＶからVIII族の金属、例え
ば、ニッケル、コバルト、モリブデン、鉄、銅、バナジ
ウム等が挙げられる。本発明で用いる触媒は、金属であ
ることができる他、金属の化合物、例えば金属ホウ化
物、金属硫化物、金属酸化物等であることができ、カー
ボンナノチューブの合成に触媒作用を有するものであれ
ばどのようなものでもよい。本発明の場合、その触媒は
有機溶媒中に超微粒子状で分散させる。その平均粒径
は、通常、０．４〜３０ｎｍ、好ましくは０．６〜２０
ｎｍ、より好ましくは１〜１０ｎｍ程度である。その触
媒超微粒子の分散液中濃度は０．０１〜２０重量％、好
ましくは０．１〜１０重量％である。その溶媒として
は、各種の有機溶媒が用いられる。有機溶媒には、アル
コール、ケトン、エステル、炭化水素等が包含される。
その具体例としては、メタノール、プロピルアルコー
ル、アミルアルコール、ヘキサノール、シクロヘキサノ
ール、ヘプタノール、オクチルアルコール、シクロヘキ
サン、メチルエチルケトン、ジエチルケトン、シクロヘ
プタン、ｎ−ヘキサン、ｎ−ヘプタン、イソオクタン、
ｎ−デカン、ベンゼン、トルエン、キシレン等が挙げら
れる。本発明では、その沸点が５０〜２００℃の範囲に
ある有機溶媒、特に、芳香族系炭化水素溶媒（ベンゼ
ン、トルエン、キシレン等）の使用が好ましい。本発明
で用いる触媒分散液において、その触媒超微粒子の粒径
分布は、できるだけシャープなものであることが好まし
い。本発明においては、触媒超微粒子の平均粒径をＭと
したときに、０．５Ｍ〜２Ｍ、好ましくは０．８Ｍ〜
１．２Ｍの粒径の範囲内に、全粒子の８０重量％以上、
好ましくは９０重量％以上、より好ましくは９５重量％
以上が存在することが好ましい。このようなシャープな
粒径分布の触媒超微粒子を含む触媒分散液を用いること
により、直径分布がシャープなカーボンナノチューブを
得ることができる。BEST MODE FOR CARRYING OUT THE INVENTION The catalyst used in the present invention has a catalytic action on the synthesis of carbon nanotubes. A transition metal is usually used as such a catalyst.
Examples of the catalyst metal include metals in the V to VIII groups, such as nickel, cobalt, molybdenum, iron, copper, and vanadium. The catalyst used in the present invention may be a metal, or a compound of a metal, for example, a metal boride, a metal sulfide, or a metal oxide. Anything may be used. In the case of the present invention, the catalyst is dispersed in the form of ultrafine particles in an organic solvent. The average particle size is usually 0.4 to 30 nm, preferably 0.6 to 20 nm.
nm, more preferably about 1 to 10 nm. The concentration of the ultrafine catalyst particles in the dispersion is 0.01 to 20% by weight, preferably 0.1 to 10% by weight. Various organic solvents are used as the solvent. Organic solvents include alcohols, ketones, esters, hydrocarbons, and the like.
Specific examples thereof include methanol, propyl alcohol, amyl alcohol, hexanol, cyclohexanol, heptanol, octyl alcohol, cyclohexane, methyl ethyl ketone, diethyl ketone, cycloheptane, n-hexane, n-heptane, isooctane,
Examples include n-decane, benzene, toluene, xylene and the like. In the present invention, it is preferable to use an organic solvent having a boiling point in the range of 50 to 200 ° C., in particular, an aromatic hydrocarbon solvent (benzene, toluene, xylene, etc.). In the catalyst dispersion used in the present invention, the particle size distribution of the ultrafine catalyst particles is preferably as sharp as possible. In the present invention, when the average particle size of the catalyst ultrafine particles is M, 0.5M to 2M, preferably 0.8M to
80% by weight or more of all particles within a particle size range of 1.2M;
90% by weight or more, more preferably 95% by weight
It is preferable that the above exist. By using the catalyst dispersion containing the catalyst ultrafine particles having such a sharp particle size distribution, carbon nanotubes having a sharp diameter distribution can be obtained.
【０００６】本発明の触媒分散液の調製方法としては、
触媒超微粒子を有機溶媒中に均一に分散し得る方法であ
ればよく、任意の方法を用いることができる。その好ま
しい調製方法においては、先ず、有機溶媒に界面活性剤
を加えて溶解させる。次に、この界面活性剤を含む有機
溶媒に対して、その有機溶媒に可溶性の触媒金属化合物
を添加し、溶解させる。次いで、この有機溶媒中の触媒
金属化合物を還元し、超微粒子状の不溶性触媒金属を生
成させることにより、触媒金属超微粒子を含むマイクロ
エマルジョンが得られる。前記界面活性剤としては、イ
オン性界面活性剤、好ましくはカチオン性界面活性剤や
アニオン界面活性剤が用いられる。この場合、カチオン
性界面活性剤としては、炭素数８〜２２、好ましくは１
２〜２０の長鎖アルキル基やアルケニル基を有する第４
級アンモニウム塩を用いることができる。カチオン性界
面活性剤の具体例としては、ジデシルジメチルアンモニ
ウムブロマイド、ジデシルジメチルアンモニウムクロラ
イド、ジドデシルジメチルアンモニウムブロマイド（又
はクロライド）、セチルトリメチルアンモニウムブロマ
イド（又はクロライド）、ドデシルトリメチルアンモニ
ウムブロマイド（又はクロライド）等を挙げることがで
きる。アニオン性界面活性剤の具体例としては、ジオク
チルスルホサッシネートナトリウム塩等が挙げられる。
界面活性剤の使用割合は、溶液中、１〜２０重量％、好
ましくは７〜１５重量％である。前記可溶性触媒金属化
合物としては、触媒金属のハロゲン化物（塩化物、臭化
物等）、有機酸塩（酢酸塩等）、有機錯塩（アセチルア
セテート塩等）、硝酸塩等が挙げられる。The method for preparing the catalyst dispersion of the present invention includes:
Any method can be used as long as the catalyst ultrafine particles can be uniformly dispersed in the organic solvent, and any method can be used. In a preferred preparation method, first, a surfactant is added to an organic solvent and dissolved. Next, a catalytic metal compound soluble in the organic solvent is added to and dissolved in the organic solvent containing the surfactant. Next, the catalyst metal compound in the organic solvent is reduced to generate ultrafine insoluble catalyst metal, whereby a microemulsion containing ultrafine catalyst metal particles is obtained. As the surfactant, an ionic surfactant, preferably a cationic surfactant or an anionic surfactant is used. In this case, the cationic surfactant has 8 to 22 carbon atoms, preferably 1 carbon atom.
4th having a long-chain alkyl or alkenyl group of 2 to 20
A quaternary ammonium salt can be used. Specific examples of the cationic surfactant include didecyldimethylammonium bromide, didecyldimethylammonium chloride, didodecyldimethylammonium bromide (or chloride), cetyltrimethylammonium bromide (or chloride), dodecyltrimethylammonium bromide (or chloride). And the like. Specific examples of the anionic surfactant include dioctyl sulfosuccinate sodium salt.
The usage ratio of the surfactant is 1 to 20% by weight, preferably 7 to 15% by weight in the solution. Examples of the soluble catalyst metal compound include a catalyst metal halide (chloride, bromide, etc.), an organic acid salt (acetate, etc.), an organic complex salt (acetyl acetate salt, etc.), a nitrate, and the like.
【０００７】溶液中の触媒金属化合物の還元法として
は、水素ガスを用いる還元法の他、ヒドラジンや水素化
ホウ素ナトリウム等の化学的還元剤を用いる方法が挙げ
られるが、化学的還元剤の使用が好ましい。この化学的
還元剤を用いる還元方法は、常温において、理論量の１
モル倍以上、好ましくは２〜１０モル倍の化学的還元剤
を溶液に攪拌下で添加することによって実施される。こ
の場合、その化学的還元剤は、水溶液や有機溶媒溶液の
形態で添加することができる。なお、ナノチューブの合
成時に水素ガスを使用することによって、還元前の状態
でも反応に用いることは可能である。As a method for reducing a catalytic metal compound in a solution, a method using a chemical reducing agent such as hydrazine or sodium borohydride may be used in addition to a method using hydrogen gas. Is preferred. This reduction method using a chemical reducing agent is performed at room temperature at a theoretical amount of 1%.
It is carried out by adding a chemical reducing agent at a molar ratio of at least 2 times, preferably 2 to 10 times, to the solution with stirring. In this case, the chemical reducing agent can be added in the form of an aqueous solution or an organic solvent solution. By using hydrogen gas at the time of synthesizing the nanotube, it is possible to use it for the reaction even before the reduction.
【０００８】前記のようにして得られる触媒超微粒子を
含むマイクロエマルジョンは、そのまま本発明における
触媒分散液として使用することができる。また、余分な
界面活性剤を除去して用いることも可能である。その場
合には、マイクロエマルジョン中にエタノールと水を体
積比で等量と２倍量をそれぞれ加え、界面活性剤を沈殿
させ、触媒超微粒子を含む上澄みを回収する。この上澄
みを再度溶媒で置換するか、もしくはろ過、洗浄を繰り
返すことにより界面活性剤濃度が１０重量％以下、好ま
しくは１重量％以下の触媒液を得る。その他の方法とし
て、ウルトラフィルターを用いた透析法により、超微粒
子を抽出濃縮することも可能である。The microemulsion containing ultrafine catalyst particles obtained as described above can be used as it is as a catalyst dispersion in the present invention. Moreover, it is also possible to remove the excess surfactant before use. In that case, ethanol and water are added to the microemulsion at an equal volume and twice the volume, respectively, to precipitate the surfactant, and the supernatant containing the ultrafine catalyst particles is recovered. The supernatant is replaced with a solvent again, or filtration and washing are repeated to obtain a catalyst solution having a surfactant concentration of 10% by weight or less, preferably 1% by weight or less. As another method, ultrafine particles can be extracted and concentrated by a dialysis method using an ultrafilter.
【０００９】本発明による他の好ましい触媒分散液の調
製方法においては、水溶性の触媒金属化合物をあらかじ
め水溶液とし、この水溶液を界面活性剤の存在下で有機
溶媒中に超微粒子状で分散させ、得られたマイクロエマ
ルジョンを前記と同様にして後処理することにより実施
される。水溶液中の触媒金属化合物の濃度は、０．０５
〜０．０００１モル／リットル以下、好ましくは０．０
０５〜０．０００５モル／リットル以下である。In another preferred method for preparing a catalyst dispersion according to the present invention, a water-soluble catalytic metal compound is previously prepared as an aqueous solution, and this aqueous solution is dispersed in the form of ultrafine particles in an organic solvent in the presence of a surfactant. The microemulsion obtained is post-treated in the same manner as described above. The concentration of the catalytic metal compound in the aqueous solution is 0.05
~ 0.0001 mol / l or less, preferably 0.0
It is 0.05 to 0.0005 mol / liter or less.
【００１０】前記においては、液中に溶解する触媒金属
化合物を還元し、金属状態に還元する方法を示したが、
この還元法による金属への還元に代えて、金属水酸化物
や、金属酸化物、金属硫化物等の不溶性金属化合物の沈
殿を生成させる通常の沈殿法も採用することができる。
その他にも、金属基板を加熱し、その蒸気を界面活性剤
のスプレーでトラップして分散液とするガス中蒸発法、
大気圧下でのエアロゾルを利用する方法、金属脂肪酸を
熱で分解して超微粒子を得る方法等も適用可能である。In the above, a method has been described in which a catalytic metal compound dissolved in a liquid is reduced to a metallic state.
Instead of the reduction to the metal by the reduction method, an ordinary precipitation method for generating a precipitate of an insoluble metal compound such as a metal hydroxide, a metal oxide, and a metal sulfide can also be employed.
In addition, a gas evaporation method in which a metal substrate is heated and its vapor is trapped by a spray of a surfactant to form a dispersion liquid,
A method using an aerosol under atmospheric pressure, a method of decomposing metal fatty acids by heat to obtain ultrafine particles, and the like are also applicable.
【００１１】本発明の触媒分散液を用いてカーボンナノ
チューブを製造するには、その触媒分散液を、７００〜
１５００℃、好ましくは１１００〜１３００℃に加熱し
た加熱炉に供給して、該有機溶媒を熱分解させる。In order to produce carbon nanotubes using the catalyst dispersion of the present invention, the catalyst dispersion is prepared in
The organic solvent is supplied to a heating furnace heated to 1500 ° C., preferably 1100 to 1300 ° C. to thermally decompose the organic solvent.
【００１２】触媒分散液を熱分解させる方法としては、
従来公知の方法が用いられる。このような方法には、電
気炉等による通常の加熱方法、マイクロ波による加熱方
法、レーザ加熱方法等が包含される。前記触媒分散液を
熱分解する場合、その反応系内には水素ガスやアルゴン
ガスをキャリアーガスとして混入することができる。そ
のキャリアーガス中に硫化水素やアンモニアなどのイオ
ウ化合物や窒素化合物を加えることができる。また、触
媒分散液にも、粉末硫黄やチオフェン等のイオウ化合物
やピリジンなどの窒素化合物を適量加えることができ
る。As a method for thermally decomposing the catalyst dispersion,
A conventionally known method is used. Such methods include a normal heating method using an electric furnace or the like, a heating method using a microwave, a laser heating method, and the like. When the catalyst dispersion is thermally decomposed, a hydrogen gas or an argon gas can be mixed into the reaction system as a carrier gas. A sulfur compound such as hydrogen sulfide or ammonia or a nitrogen compound can be added to the carrier gas. An appropriate amount of a sulfur compound such as powdered sulfur or thiophene or a nitrogen compound such as pyridine can be added to the catalyst dispersion.
【００１３】加熱炉としては、横型及び縦型のいずれの
型のものを用いることができる。加熱炉に対する触媒分
散液の供給は、滴下法やスプレー法等の各種の方法で行
うことができる。前記のようにして、加熱炉内には、カ
ーボンナノチューブが生成される。このカーボンナノチ
ューブは、触媒超微粒子を基体として成長したもので、
その太さ（直径）は、触媒超粒子の粒径に依存し、その
触媒超粒子の粒径とほぼ一致する。従って、本発明の場
合、触媒超微粒子として、粒径均一性の良いものを用い
ることにより、その太さの均一性の良いカーボンナノチ
ューブを得ることができる。また、触媒超微粒子とし
て、粒子の小さいもの、例えば、その粒径が１ｎｍ程度
の超微粒子を用いることにより、その直径が１ｎｍ程度
の極めて細いカーボンナノチューブを得ることができ
る。本発明によれば、その直径が約０．４〜３０ｎｍ程
度のカーボンナノチューブを容易に得ることができる。
本発明においては、触媒分散液における分散媒（有機溶
媒）が炭素原料として熱分解を受け、カーボンナノチュ
ーブを与えることから、本発明の方法は容易にかつ安価
に実施することができ、カーボンナノチューブの大量生
産法としてすぐれたものである。As the heating furnace, any of a horizontal type and a vertical type can be used. Supply of the catalyst dispersion to the heating furnace can be performed by various methods such as a dropping method and a spray method. As described above, carbon nanotubes are generated in the heating furnace. This carbon nanotube is grown using catalyst ultrafine particles as a substrate.
The thickness (diameter) depends on the particle size of the catalyst superparticle, and substantially matches the particle size of the catalyst superparticle. Therefore, in the case of the present invention, carbon nanotubes having a uniform thickness can be obtained by using the catalyst ultrafine particles having a good particle size uniformity. Also, by using ultra-fine particles having a small particle size, for example, ultra-fine particles having a particle size of about 1 nm as the catalyst ultra-fine particles, extremely thin carbon nanotubes having a diameter of about 1 nm can be obtained. According to the present invention, carbon nanotubes having a diameter of about 0.4 to 30 nm can be easily obtained.
In the present invention, since the dispersion medium (organic solvent) in the catalyst dispersion undergoes thermal decomposition as a carbon material to give carbon nanotubes, the method of the present invention can be carried out easily and inexpensively. It is an excellent mass production method.
【００１４】[0014]
【実施例】次に本発明を実施例によりさらに詳細に説明
する。Next, the present invention will be described in more detail with reference to examples.
【００１５】実施例１ トルエン９０ｇ中にカチオン性界面活性剤であるジデシ
ルジメチルアンモニウムブロマイド（ＤＤＡＢ）を１０
ｇ溶かし２時間攪拌する。次に塩化コバルト六水和物１
ｇを溶液中に導入し、さらに３時間攪拌する。この溶液
は透明な水色を示す。その後、１０ｍｏｌ／ｌの水素化
ホウ素ナトリウム水溶液を１ｍｌ滴下して塩化コバルト
を還元する。滴下後、溶液は黒く懸濁しコロイド溶液と
なるこの溶液にエタノールを等量、次いで水を２倍量加
えると余分な界面活性剤が沈殿し超微粒子のみが回収で
きる。これをトルエンで再度置換し、精製を行うことも
可能である。このようにして得られた触媒分散液におい
て、そのコバルト粒子の平均粒径は、約４ｎｍである。
反応直前に、この触媒液にチオフェンを１ｗｔ％加え
る。次に、この触媒分散液を、１２００℃に加熱した縦
型の加熱炉内に滴下した。この場合の加熱炉は、内径２
６ｍｍ、長さ１０００ｍｍの石英管の外周に電熱コイル
を配設したもので、その上端開口は、液体供給ノズルと
ガス供給ノズルを有する蓋体で密封したものであり、そ
の下端開口は、ナノチューブ回収部が接続されておりガ
ス排出管を有する蓋体で密封したものである。前記ガス
供給ノズルからは、水素ガスを１２００ｃｃ／分で導入
するとともに、その液体供給ノズルからは、前記触媒分
散液を８０μｌ／分の速度で供給した。前記のようにし
て、６０分間反応を行ったところ、その炉底には、カー
ボンナノチューブ０．１ｇが得られた。そしてカーボン
ナノチューブの平均内径は約４ｎｍ〜１０ｎｍと超微粒
子の直径に対応していることがわかった。EXAMPLE 1 Didecyldimethylammonium bromide (DDAB), a cationic surfactant, was added to 10 g of toluene in 90 g of toluene.
g and stir for 2 hours. Next, cobalt chloride hexahydrate 1
g are introduced into the solution and stirred for a further 3 hours. This solution shows a clear light blue color. Thereafter, 1 ml of a 10 mol / l sodium borohydride aqueous solution is added dropwise to reduce cobalt chloride. After dropping, the solution becomes black and becomes a colloidal solution. When an equal amount of ethanol and then twice the amount of water are added to this solution, excess surfactant is precipitated and only ultrafine particles can be recovered. This can be replaced with toluene again for purification. In the catalyst dispersion thus obtained, the average particle size of the cobalt particles is about 4 nm.
Immediately before the reaction, 1 wt% of thiophene is added to this catalyst solution. Next, this catalyst dispersion was dropped into a vertical heating furnace heated to 1200 ° C. The heating furnace in this case has an inner diameter of 2
An electric heating coil is arranged on the outer periphery of a 6 mm, 1000 mm long quartz tube, the upper end opening of which is sealed with a lid having a liquid supply nozzle and a gas supply nozzle, and the lower end opening thereof is used for collecting nanotubes. The parts are connected and sealed with a lid having a gas discharge pipe. Hydrogen gas was introduced at 1200 cc / min from the gas supply nozzle, and the catalyst dispersion was supplied at a rate of 80 μl / min from the liquid supply nozzle. When the reaction was carried out for 60 minutes as described above, 0.1 g of carbon nanotubes was obtained at the bottom of the furnace. The average inner diameter of the carbon nanotube was found to be about 4 nm to 10 nm, which corresponded to the diameter of the ultrafine particles.
【００１６】[0016]
【発明の効果】本発明によれば、カーボンナノチューブ
を効率よく生産することができる。しかも、その生産設
備は、構造上簡単なものでよいことから、そのコストは
安価である。According to the present invention, carbon nanotubes can be efficiently produced. In addition, the cost of the production equipment is low because it can be simple in structure.
───────────────────────────────────────────────────── フロントページの続き (71)出願人 597045538 大嶋 哲 千葉県我孫子市並木５−２−17 (72)発明者 吾郷 浩樹 茨城県つくば市東１丁目１番 経済産業省 産業技術総合研究所物質工学工業技術研究 所内 (72)発明者 湯村 守雄 茨城県つくば市東１丁目１番 経済産業省 産業技術総合研究所物質工学工業技術研究 所内 (72)発明者 大嶋 哲 茨城県つくば市東１丁目１番 経済産業省 産業技術総合研究所物質工学工業技術研究 所内 Ｆターム(参考） 4G046 CA00 CC01 CC03 CC08 4G069 AA02 AA08 BB02B BC67B CD10 DA08 EA01X EA01Y EB18X EB18Y EB19 FA01 FB05 FB08 FB45 4L037 CS03 CS04 CT02 CT41 CT43 FA02 PA06 PA07 PA13 ────────────────────────────────────────────────── ─── Continuing from the front page (71) Applicant 597045538 Satoshi Oshima 5-2-17 Namiki, Abiko, Chiba Pref. (72) Inventor Hiroki Ago 1-1-1, Higashi, Tsukuba, Ibaraki Pref. Institute of Industrial Technology (72) Inventor Morio Yumura 1-1-1, Higashi, Tsukuba, Ibaraki Pref., Ministry of Economy, Trade and Industry (72) Inventor Tetsu Oshima 1-1-1, Higashi, Tsukuba, Ibaraki, Economy, Trade and Industry 4G046 CA00 CC01 CC03 CC08 4G069 AA02 AA08 BB02B BC67B CD10 DA08 EA01X EA01Y EB18X EB18Y EB19 FA01 FB05 FB08 FB45 4L037 CS03 CS04 CT02 PA13 PA07
Claims (1)
微粒子を有機溶媒中に分散させて形成した触媒分散液
を、７００〜１５００℃に加熱した加熱炉内に供給し
て、該有機溶剤を分解させることを特徴とするカーボン
ナノチューブの製造方法。1. A catalyst dispersion formed by dispersing catalyst ultrafine particles having a particle size of 0.4 to 30 nm in an organic solvent is supplied into a heating furnace heated to 700 to 1500 ° C. A method for producing carbon nanotubes, comprising decomposing a solvent.
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|---|---|---|---|
| JP2001014981A JP2002220214A (en) | 2001-01-23 | 2001-01-23 | Method for manufacturing carbon nano tube |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001014981A JP2002220214A (en) | 2001-01-23 | 2001-01-23 | Method for manufacturing carbon nano tube |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002306230A Division JP2003137519A (en) | 2002-10-21 | 2002-10-21 | Catalyst dispersion for production of carbon nanotube and its production method |
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ID=18881602
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005225757A (en) * | 2001-07-20 | 2005-08-25 | Kh Chemicals Co Ltd | Process for preparation of carbon nanotube |
| US7485348B2 (en) * | 2003-11-17 | 2009-02-03 | Konica Minolta Holdings, Inc. | Method for forming nanostructured carbons, nanostructured carbons and a substrate having nanostructured carbons formed thereby |
| JP2009507744A (en) * | 2005-05-05 | 2009-02-26 | 本田技研工業株式会社 | Synthesis of narrow-diameter carbon single-walled nanotubes |
| JP2011057551A (en) * | 2010-11-08 | 2011-03-24 | Osaka Prefecture Univ | Method and apparatus for producing carbon nanostructure |
| JP2011173743A (en) * | 2010-02-23 | 2011-09-08 | Toyo Univ | Method for manufacturing carbon nanotube |
| WO2019164225A1 (en) * | 2018-02-20 | 2019-08-29 | 한국과학기술원 | Method for manufacturing carbon nanotubes doped with heteroatoms from carbon dioxide |
-
2001
- 2001-01-23 JP JP2001014981A patent/JP2002220214A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005225757A (en) * | 2001-07-20 | 2005-08-25 | Kh Chemicals Co Ltd | Process for preparation of carbon nanotube |
| US7329398B2 (en) | 2001-07-20 | 2008-02-12 | Kh Chemicals Co., Ltd. | Preparation of carbon nanotubes |
| US7485348B2 (en) * | 2003-11-17 | 2009-02-03 | Konica Minolta Holdings, Inc. | Method for forming nanostructured carbons, nanostructured carbons and a substrate having nanostructured carbons formed thereby |
| JP2009507744A (en) * | 2005-05-05 | 2009-02-26 | 本田技研工業株式会社 | Synthesis of narrow-diameter carbon single-walled nanotubes |
| JP2011173743A (en) * | 2010-02-23 | 2011-09-08 | Toyo Univ | Method for manufacturing carbon nanotube |
| JP2011057551A (en) * | 2010-11-08 | 2011-03-24 | Osaka Prefecture Univ | Method and apparatus for producing carbon nanostructure |
| WO2019164225A1 (en) * | 2018-02-20 | 2019-08-29 | 한국과학기술원 | Method for manufacturing carbon nanotubes doped with heteroatoms from carbon dioxide |
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